title: Metal-dependent and redox-selective coordination behaviors of metalloligand [MoV(1,2-benzenedithiolato)3]- with CuI/AgI ions.
abstract: The synthesis and characterization of two coordination polymers, {Cu(I)[Mo(V)(bdt)(3)]·0.5Et(2)O}(n) (1·0.5Et(2)O, bdt: o-benzenedithiolato) and {Ag(I)[Mo(V)(bdt)(3)]}(n) (2), composed of redox-active [Mo(V)(bdt)(3)](-) metalloligand with Cu(I) and Ag(I) ions are reported. The complexation reactions of [Mo(V)(bdt)(3)](-) with Cu(II)(ClO(4))(2) or Ag(I)ClO(4) commonly lead to the formation of one-dimensional (1-D) coordination polymers. The presence of Cu(I) in 1·0.5Et(2)O strongly indicates that the Cu(II) ion is reduced during the complexation reaction with [Mo(V)(bdt)(3)](-), which acts as an electron donor. The total dimensionalities of the assembled structures of 1·0.5Et(2)O and 2 are significantly different and related to the type of additional metal ions, Cu(I) and Ag(I). In contrast to the isolated 1-D chain structure of 1·0.5Et(2)O, complex 2 has a three-dimensional (3-D) assembled structure constructed from additional π-π stacking interactions between adjacent [Mo(V)(bdt)(3)](-) moieties. These structural differences influence the solubility of the complexes in organic solvents; complex 1·0.5Et(2)O is soluble as origomeric species in highly polar solvents, while 2 is insoluble in organic solvents and water. Coordination polymers 1·0.5Et(2)O and 2 were investigated by UV-vis spectroscopy in the solid state, and that in solution together with their electrochemical properties were also investigated for 1 because of its higher solubility in polar organic solvents. Complex 1·0.5Et(2)O dissolved in CH(3)CN demonstrates concentration-dependent UV-vis spectra supporting the presence of coordinative interactions between [Mo(V)(bdt)(3)](-) moieties and Cu(I) ions to create the origomeric species even in solutions, an observation that is supported also by electrochemical experiments.
authors.affiliation: Center for Strategic Utilization of Elements, Hokkaido University, Kita-ku, Sapporo, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Matsumoto
authors.forename: Ho-Chol
authors.initials: HC
authors.lastname: Chang
authors.forename: Atsushi
authors.initials: A
authors.lastname: Kobayashi
authors.forename: Kohei
authors.initials: K
authors.lastname: Uosaki
authors.forename: Masako
authors.initials: M
authors.lastname: Kato
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007454:Iodides / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D018030:Silver Compounds / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D007454:Iodides; D007477:Ions; D008024:Ligands; D009942:Organometallic Compounds; D018030:Silver Compounds; D013438:Sulfhydryl Compounds; D003300:Copper; C073870:cuprous iodide; D008982:Molybdenum; C030584:silver iodide